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Volumn 63, Issue 3, 1998, Pages 602-607

Regioselective Porphyrin Bridge Cleavage Controlled by Electronic Effects. Coupled Oxidation of 3-Demethyl-3-(trifluoromethyl)mesohemin IX and Identification of Its Four Biliverdin Derivatives

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EID: 0000632097     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9714728     Document Type: Article
Times cited : (29)

References (34)
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    • For a detailed description of pyrrole pigment nomenclature, see: Nomenclature of Tetrapyrroles, Recommendations of 1986, International Union of Pure and Applied Chemistry and International Union of Biochemistry, Joint Commission on Biochemical Nomenclature. Pure Appl. Chem. 1987, 59, 779-832.
    • (1987) Pure Appl. Chem. , vol.59 , pp. 779-832
  • 3
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    • Heme-Cleavage: Biological Systems and Chemical Analogues
    • Smith, K. M., Ed.; Elsevier Scientific Publishing Co.: Amsterdam
    • (b) O'Carra, P. Heme-Cleavage: Biological Systems and Chemical Analogues. Porphyrins and Metalloporphyrins; Smith, K. M., Ed.; Elsevier Scientific Publishing Co.: Amsterdam; 1975; pp 123-153.
    • (1975) Porphyrins and Metalloporphyrins , pp. 123-153
    • O'Carra, P.1
  • 4
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    • Dolphin, D., Eds.; Academic Press: New York
    • Schmid, R.; McDonagh, A. F. In The Porphyrins; Dolphin, D., Eds.; Academic Press: New York, 1979; Vol. 6, pp 257-292.
    • (1979) The Porphyrins , vol.6 , pp. 257-292
    • Schmid, R.1    McDonagh, A.F.2
  • 10
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    • note
    • +.
  • 12
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    • Dolphin, D., Eds.; Academic Press: New York
    • McDonagh, A. F. In The Porphyrins; Dolphin, D., Eds.; Academic Press: New York, 1979; Vol. 6, pp 293-491.
    • (1979) The Porphyrins , vol.6 , pp. 293-491
    • McDonagh, A.F.1
  • 14
    • 1542658913 scopus 로고    scopus 로고
    • note
    • It is known that some published results are incorrect due to preferential isolation of isomers during workup steps. See ref 2b and references cited therein.
  • 15
    • 1542553823 scopus 로고    scopus 로고
    • The calculations were carried out with Spartan version 3.1.2., Wavefunction Inc.
    • The calculations were carried out with Spartan version 3.1.2., Wavefunction Inc.
  • 16
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    • Pullman, B.; Perault, A.-M. Proc. Natl. Acad. Sci. U.S.A. 1959, 45, 1476-1480. However, in normal heme the electronic effects caused by the substituents are not strong enough to show a pronounced regioselectivity in the coupled oxidation process in the absence of the protein.
    • (1959) Proc. Natl. Acad. Sci. U.S.A. , vol.45 , pp. 1476-1480
    • Pullman, B.1    Perault, A.-M.2
  • 24
    • 0025708347 scopus 로고
    • Of the four synthetic meso-hydroxyhemes only the α-isomer was efficiently converted to biliverdin by heme oxygenase. However, the fate of the δ-, γ-, and β-meso-hydroxy isomers of other porphyrins formed in situ is not clear. See: Yoshinaga, T.; Sudo, Y.; Sano, S. Biochem. J. 1990, 270, 659-664.
    • (1990) Biochem. J. , vol.270 , pp. 659-664
    • Yoshinaga, T.1    Sudo, Y.2    Sano, S.3
  • 27
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    • Torpey, J.; Ortiz de Montellano, P. R. J. Biol. Chem. 1996, 271, 26067-26073. Some of the conclusions in that paper are based on the undetection of 10-methyl-substituted biliverdins. It is described that such kind of biliverdins readily tautomerize to a bilirubinoid structure that presents different absorption and Chromatographie properties. For examples see ref 10, pp 245-246.
    • (1996) J. Biol. Chem. , vol.271 , pp. 26067-26073
    • Torpey, J.1    Ortiz De Montellano, P.R.2
  • 28
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    • note
    • Frydman and Frydman described the structural requirements of the substrate involved in the specificity of heme oxygenase, the presence of the vicinal propionic acid chains being the most important requirement (see ref 26). Electron-withdrawing groups at the β-position of rings A and B decreased substrate activity but did not suppress it.
  • 31
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    • note
    • 19F NMR spectroscopy as described in this paper, those products can be easily determined and quantified without any purification.


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